1652
Inorg. Chem. 1997, 36, 1652-1656
Metal-Purine Interactions: Homo- and Heterodinuclear Platinum(II) and/or Palladium(II) Complexes of 8-Thiotheophylline. Crystal Structures of [Pt(µ-TT)(dppm)]2‚2DMSO and [(dppm)Pt(µ-TT)2Pd(dppm)]‚7H2O Enrique Colacio,* Rafael Cuesta, Mustapha Ghazi, M. Angeles Huertas, Jose M. Moreno, and Antonio Navarrete Departamento de Quı´mica Inorga´nica, Facultad de Ciencias, Universidad de Granada, 18071 Granada, Spain ReceiVed October 24, 1996X
The reaction of cis-[MCl2(dppm)] (M ) Pt(II) and Pd(II); dppm ) bis(diphenylphosphino)methane) with H2TT and NaOH (H2TT ) 8-thiotheophylline) yields neutral mononuclear [M(HTT-S(8))2(dppm)] complexes. Homodinuclear [M(µ-TT-N(7),S(8))(dppm)]2 (M ) Pt(II) and Pd(II)) are prepared either by the reaction of [M(HTT)2(dppm)] with cis-[MCl2(dppm)] and NaOH or by the direct reaction of cis-[MCl2(dppm)] with Na2TT, prepared in situ from H2TT and NaOH. The crystal structure of the Pt derivative is reported: [Pt(µ-TT)(dppm)]2‚2DMSO (3) crystallizes in the triclinic space group P1h with a ) 12.949(3) Å, b ) 13.009(3) Å, c ) 22.980(5) Å, R ) 96.89(3)°, β ) 103.53(3)°, γ ) 106.43(3)°, Z ) 2, and R1 ) 0.045. Heterodinuclear [(dppm)Pt(µ-TT)2Pd(L-L)] complexes are obtained by reaction of [Pt(HTT)2(dppm)] with [PdCl2(L-L)] in basic medium (L-L ) dppm and 2,2′-bipyridine). The crystal structure of [(dppm)Pt(µ-TT)2Pd(dppm)]‚7H2O (5) is reported. The complex crystallizes in the orthorhombic space group P212121 with a ) 16.560(5) Å, b ) 17.063(5) Å, c ) 24.428(5) Å, Z ) 4, and R1 ) 0.042. The structures of 3 and 5 are almost identical, by which 5 can be seen as an isomorphic substitution of one of the Pt(II) ions of 3 by a Pd(II) ion. The structures consist of dinuclear units having a pseudo-2-fold axis perpendicular to that defined by the metal atoms. The two metal atoms are bibridged by two µ-TT-N(7),S(8) ligands, in a head to tail arrangement. The square-planar coordination of the metal atoms is completed by a chelate dppm ligand. The steric repulsions between the bulky dppm ligands must be the main factor precluding metal-metal interaction in these compounds.
Introduction Thiolated purines are of interest because some of them, such as 6-mercaptopurine and 6-mercaptoguanine, are established clinical agents for the therapy of human leukemias.1 In some cases metal complexes of these bases, especially those of Pt(II) and Pd(II), show higher anticancer activity than the free ligand.2 On the other hand, phosphines and phosphine metal containing complexes have received much attention during the past few years due to their potential use as antitumor agents.3 Particularly, 1,2-bis(diphenylphosphino)ethane (dppe) and some of its analogues have been shown to have antitumor activity against a wide range of tumors, and, moreover, their activity is enhanced upon coordination to metal ions, such as gold(I). The possibility that thiolated purines may act in a synergetic fashion with [M(diphosphine)]2+ moieties, giving rise to a bifunctional antitumor agent, prompted us to prepare and characterize purine-metal-phosphine complexes. As a continuation of our studies along this line,4 herein we report on the preparation, characterization, and reactivity of a number of X Abstract published in AdVance ACS Abstracts, March 15, 1997. (1) (a) Wood, H. B., Jr. Cancer Chemother. Rep., Part 3 1971, 2, 9. (b) Williams, D. R. Chem. ReV. 1972, 72, 203. (c) Zubrod, C. G. Life Sci. 1974, 14, 809. (d) Mautner, H. G.; Chu, S.-H.; Jaffe, J. J.; Sartorelli, A. C. J. Med. Chem. 1963, 6, 36. (e) Van Scoik, K. G.; Johnson, C. A.; Porter, W. R. Drug. Metab. ReV. 1985, 16, 157. (2) (a) Kirschner, S.; Wei, Y. K.; Francis, D.; Bergman, J. G. J. Med. Chem. 1969, 9, 369. (b) Skinner, S. M.; Swatzell, J. M.; Lewis, R. W. Res. Commum. Chem. Pathol. Pharmacol. 1978, 19, 165. (c) Das, M.; Livinstone, S. E. Br. J. Cancer 1978, 38, 325. (d) Maeda, M.; Abiko, N.; Sasaki, T. J. Med. Chem. 1981, 24, 167. (3) (a) Berners-Price, S. J.; Sadler, P. J. Chem. Br. 1987, 23, 541. (b) Berners-Price, S. J.; Sadler, P. J. Struct. Bonding 1988, 70, 27. (c) Sadler, P. J. AdV. Inorg. Chem. Radiochem. 1991, 36, 1.
S0020-1669(96)01288-8 CCC: $14.00
Pt(II) and Pd(II) complexes with 8-thiotheophylline (hereafter H2TT). Experimental Section The purine derivative 1,3-methyl-8-thioxanthine (8-thiotheophylline) was prepared according to literature procedures,5 while bis(diphenylphosphino)methane (dppm) was purchased from Aldrich and used as received. The compounds [PtCl2(dppm)] and [PdCl2(dppm)] were prepared by standard methods.6 [PtCl2(bipy)] and [PdCl2(bipy)] were prepared by procedures described for the related complexes with ethylenediamine.7 Physical Measurements. Microanalyses and IR spectra were obtained as already described.4 The 31P-NMR spectra were obtained in dimethyl-d6 sulfoxide (DMSO-d6) at 298 K on a Bruker AM-300 operating at 121.42 MHz and using H3PO4 (85% (w/w) in D2O) as external standard. Preparations. [Pt(HTT)2(dppm)] (1). This complex can be prepared by following these methods: (a) To a solution of [PtCl4(NH3)2] (0.282 g, 0.76 mmol) in ethanol (50 mL) was added H2TT (0.424 g, 2.0 mmol). The suspension was stirred until a clear solution was obtained. After filtration of any amount of insoluble material, the resulting orange solution was allowed to stand at room temperature, whereupon the dark-orange product [Pt(HTT)2(NH3)Cl] formed. This complex (0.1 g, 0.15 mmol) and dppm (0.13 g, 0.3 mmol) were stirred (4) (a) Colacio, E.; Romerosa, A.; Ruiz, J.; Roma´n, P.; Gutie´rrez-Zorrilla, J. M.; Martı´nez-Ripoll, M. J. Chem. Soc., Dalton. Trans. 1989, 2323. (b) Colacio, E.; Romerosa, A.; Ruiz, J.; Roma´n, P.; Gutie´rrez-Zorrilla, J. M.; Vega, A.; Martı´nez-Ripoll, M. Inorg. Chem. 1991, 30, 3743. (c) Colacio, E.; Cuesta R.; Gutie´rrez-Zorrilla, J. M.; Luque, A.; Roma´n, P.; Giraldi, T.; Taylor, M. R. Inorg. Chem. 1996, 35, 4232. (5) Merz, K. W.; Stahl, P. H. Arzneim.-Forsch. 1965, 15, 10. (6) (a) Church, M. J.; Mays, M. J. J. Inorg. Nucl. Chem. 1971, 33, 253. (b) Booth, G.; Chatt, J. J. Chem. Soc. A 1966, 364. (c) Steffen, W. L.; Palenik, G. J. Inorg. Chem. 1976, 15, 2432. (7) Hohmann, H.; van Eldik, R. Inorg. Chim. Acta 1990, 174, 87.
© 1997 American Chemical Society
Pt(II) and/or Pd(II) Complexes of H2TT and heated in ethanol (50 mL) until a clear yellow solution was obtained. This solution, kept at room temperature for several days, gave yellow needlelike crystals of 1; yield, 70%. (b) To a solution of H2TT (0.12 g, 0.3 mmol) in 5 mL of water containing 0.3 mmol of NaOH was added a suspension of [PtCl2(dppm)] (0.1 g, 0.15 mmol) in ethanol (50 mL). The reaction mixture was warmed for 15 min to give a light yellow solution from which, after evaporation at room temperature, yellow needlelike crystals of 1 were formed; yield, 80%. Anal. Calcd for C39H36N8O4P2S2Pt: C, 46.75; H, 3.62; N, 11.18; S, 6.40. Found: C, 46.29; H, 3.72; N, 10.99; S, 6.50. [Pd(HTT)2(dppm)]‚4H2O (2). The complex [PdCl2(dppm)] (0.1 g, 0.18 mmol) and H2TT (0.08 g, 0.36 mmol) were reacted by using the preceding b procedure to yield orange crystals; yield, 75%. Anal. Calcd for C39H44N8O8P2S2Pd: C, 47.54; H, 4.50; N, 11.37; S, 6.51. Found: C, 47.42; H, 4.33; N, 10.91; S, 6.10. [Pt(µ-TT)(dppm)]2‚2DMSO (3). This complex can be obtained by following two different procedures: (a) A suspension of [PtCl2(dppm)] (0.1 g, 0.15 mmol) in ethanol (50 mL) was added to a solution of H2TT (0.03 g, 0.15 mmol) in 5 mL of water containing 0.3 mmol of NaOH. After the mixture was warmed for 15 min, a yellow light solution was obtained, which, kept at room temperature, yielded a yellow precipitate, which was washed with ethanol and diethyl ether. Recrystallization from DMSO gave yellow crystals; yield, 70%. (b) To a suspension of [PtCl2(dppm)] (0.1 g, 0.15 mmol) in 30 mL of ethanol were added 1 (0.15 g, 0.15 mmol) and NaOH (12 mg, 0.3 mmol). The reaction mixture was heated to reflux for 15 min to give a light yellow solution, which, kept at room temperature, provided a yellow precipitate of 3. Anal. Calcd for C36H40N4O4P2S3Pt: C, 47.06; H, 3.95; N, 6.46; S, 7.39. Found: C, 47.58; H, 3.88; N, 6.48; S, 7.60. [Pd(µ-TT)(dppm)]2‚3H2O (4). This complex was prepared either from [PdCl2(dppm)] and H2TT or from 2 and [PdCl2(dppm)], by using the procedures described for 3, as orange crystals. Anal. Calcd for C32H34N4O5P2SPd: C, 52.79; H, 4.29; N, 7.70; S, 4.40. Found: C, 52.16; H, 4.20; N, 7.58; S, 4.75. [PtPd(µ-TT)2(dppm)2]‚7H2O (5). Complex 1(0.15 g, 0.15 mmol) and [PdCl2(dppm)] (0.08 g, 0.15 mmol) were reacted in ethanol using the same procedure (b) as that for 3; yield, 70%. Anal. Calcd for C64H70N8O11P4S2PdPt: C, 47.54; H, 4.36; N, 6.93; S, 3.97. Found: C, 48.03; H, 4.18; N, 6.63; S, 3.75. [Pt2(µ-TT)2(dppm)(bipy)] (6). To a stirred suspension of [Pt(HTT)2(dppm)] (0.15 g, 0.15 mmol) in 50 mL of MeOH/H2O (80% (w/w)) was added [PtCl2(bipy)] (0.06 g, 0.15 mmol). Then, NaOH (0.30 mmol) was added and the reaction mixture heated to reflux for 15 min; the color of the solution changed from yellow to orange. Evaporation of the resulting solution at room temperature led to an orange powder, which was washed with methanol and diethyl ether; yield, 60%. Anal. Calcd for C49H42N10O4P2S2Pt2: C, 43.56; H, 3.13; N, 10.37; S, 4.75. Found: C, 43.08; H, 2.96; N, 10.85; S, 4.27. [PtPd(µ-TT)2(dppm)(bipy)] (7). The complexes [Pt(HTT)2(dppm)] (0.15 g, 0.15 mmol) and [PdCl2(bipy)] (0.05 g, 0.15 mmol) were reacted, in MeOH/H2O, by using the preceding procedure to give an orange powder; yield, 59%. Anal. Calcd for C49H42N10O4P2S2PdPt: C, 46.62; H, 3.35; N, 11.09; S, 5.08. Found: C, 46.43; H, 3.85; N, 10.94; S, 5.04. X-ray Data Collections and Structure Determinations. Single crystal data collections for 3 and 5 were performed at 293 K with a Siemens R3m/V diffractometer using graphite monochromatized Mo KR (λ ) 0.710 69 Å) radiation. The unit cell parameters were calculated by least-squares refinement of 25 well centered reflections in the range 15 < 2θ < 45° for 3 and 5. The data were collected by the ω/2θ scan mode. Intensities of four check reflections measured after every 120 min showed only statistical variation. The data were corrected for Lorentz and polarization effects. Absorption corrections were applied via an empirical Ψ scan. The structures were solved by direct methods and subsequent Fourier syntheses with the SHELXTL/ PC V5.0 program.8 All non-hydrogen atoms were refined anisotropically, and the positions of the hydrogen atoms were calculated with isotropic temperature factors, with the following exceptions: (a) the phenyl rings were refined as a rigid group having a common isotropic temperature factor; (b) for 3, the DMSO molecules were refined
Inorganic Chemistry, Vol. 36, No. 8, 1997 1653 Table 1. Crystal Data and Structure Refinement for 3 and 5 compd emp formula fw cryst syst space group unit cell dimens a, Å b, Å c, Å R, deg β, deg γ, deg Z vol, Å3 dens (calcd), g cm-3 abs coeff, mm-1 F(000) cryst size, mm θ range, deg limiting indices
12.949(3) 13.009(3) 22.980(5) 96.89(3) 103.53(3) 106.43(3) 2 3537.3(14) 1.630 4.215 1720 0.40 × 0.20 × 0.16 1.67-20.00 0 e h e +12 -12 e k e +12 -22 e l e +21 reflcns collecd 6976 independ reflecns 6597 [R(int) ) 0.0227] refinement method full-matrix least-squares data/params 6566/418 goodness-of-fit (F2) 1.038 R indices [I > 2σ(I)] R1 ) 0.0454, Rw2 ) 0.1024 R indices (all data) R1 ) 0.0595, Rw2 ) 0.1175 largest peak and hole 1.463 and -0.826 e‚A-3
[PtPd(µ-TT)2(dppm)2]‚ 7H2O C64H70N8O11S2P4Pd Pt 1616.77 orthorhombic P212121 16.560(5) 17.063(5) 24.428(5) 90.000(5) 90.000(5) 90.000(5) 4 6903(3) 1.556 2.501 3256 0.25 × 0.18 × 0.15 1.67-22.50 -1 e h e +17 -1 e k e +18 -1 e l e +26 6117 5848 [R(int) ) 0.0404] full-matrix least-squares 5805/446 0.883 R1 ) 0.0420, Rw2 ) 0.1071 R1 ) 0.0531, Rw2 ) 0.1557 0.839 and -0.665 e‚A-3
isotropically, having one of them be a disordered sulfur atom; and (c) for 5, the hydrogen atoms belonging to the water molecules were omitted, while the positions of both metal ions are disordered with Pt and Pd in ca. 50%. Crystal data and structure determination parameters are given in Table 1. Selected atomic coordinates and equivalent isotropic thermal parameters are listed in Table 2.
Results and Discussion The reaction of cis-[M(dppm)Cl2] (where M ) Pd(II) and Pt(II) and dppm ) 1,2-bis(diphenylphosphino)methane) with H2TT and NaOH in ethanol and a 1:2:2 molar ratio leads to complexes 1 and 2, of empirical formula [M(dppm)(HTT)2]. Interestingly, the platinum(II) complex can also be obtained from the reaction of [Pt(HTT)2][Pt(NH3)(HTT)Cl2] (prepared by reduction of K2[PtCl6] with the ligand itself) with dppm in 1:2 molar ratio (see Scheme 1). It should be pointed out that H2TT has two ionizable protons in the imidazole ring (see Scheme 1). When these protons dissociate in basic medium, the sulfur atom must be the most probable binding site, since a soft polarizable metal, such as Pt(II) and Pd(II), shows preference toward the softer S donor over the less polarizable nitrogen donor atom. The second position of coordination must be N(7) rather than N(9) because of the steric hindrance from the N(3)-CH3 group. Information about the structure of these mononuclear complexes was derived from the IR and 31P-NMR results, which confirm the S(8)-monodentate coordination of the HTT- anion in 1 and 2. Thus, the IR spectra show no S-H bands, whereas only one N-H band is observed in the 2800-3200 cm-1 region. The 31P-NMR spectra exhibit a single chemical shift (with a pair of 195Pt satellites for the platinum compound), consistent with a square-planar geometry with two equivalent cis phosphine moieties.9 Furthermore, the values of δ(2P) are similar to those (9)
(8) SHELXTL/PC V5.0; Siemens: Madison, WI, 1994.
[Pt2(µ-TT)2(dppm)2]‚ 2DMSO C68H68N8O6S4P4Pt2 1735.60 triclinic P1h
31P-NMR Spectroscopy in Stereochemical Analysis; Verkade, J. G., Quin, L. D., Eds.; VCH Publishers: New York, 1986.
1654 Inorganic Chemistry, Vol. 36, No. 8, 1997
Colacio et al.
Table 2. Selected Atomic Coordinates (×104) and U(eq) Parameters (Å2 × 103) for 3 and 5 atom
x
y
z
Scheme 1 U(eq)
Pt(1) Pt(2) P(2) P(1) P(3) P(4) S(8) C(8) N(7) N(9) C(4) C(5) C(6) O(6) N(3) C(3) C(2) O(2) N(1) C(1) S(18) C(18) N(17) N(19) C(15) C(14) N(13) C(13) C(12) O(12) N(11) C(11) C(16) O(16) C(012) C(034)
[(dppm)Pt(µ-TT)2Pt(dppm)]‚2DMSO 1716(1) 4858(1) 3381(1) 1566(1) 3259(1) 1642(1) 1053(3) 3838(3) 4011(2) 394(3) 5496(3) 3643(2) 1892(3) 1673(3) 1377(2) -77(2) 2061(2) 1072(2) 3108(3) 4065(3) 3284(1) 3676(10) 4614(9) 2721(6) 3187(7) 4238(8) 2119(4) 4668(7) 5449(8) 2857(5) 4748(10) 5604(10) 2292(6) 3889(10) 4885(10) 1838(6) 3746(11) 4958(11) 1223(7) 2985(8) 4397(8) 774(4) 4630(9) 5827(9) 1140(5) 4543(14) 5996(13) 515(7) 5516(12) 6561(11) 1593(7) 6216(9) 7296(9) 1480(5) 5589(8) 6433(9) 2179(6) 6499(12) 7188(12) 2677(7) 933(3) 4779(2) 1728(1) 2013(10) 5858(9) 2239(6) 2256(7) 5967(7) 2861(4) 2663(8) 6693(8) 2053(5) 3144(10) 6931(9) 3077(6) 3357(11) 7335(10) 2587(7) 4243(9) 8288(9) 2649(6) 4440(12) 8690(12) 2110(7) 4911(12) 8831(12) 3229(9) 5706(9) 9668(9) 3279(6) 4665(10) 8394(10) 3711(6) 5390(16) 9000(14) 4313(8) 3816(11) 7416(11) 3684(7) 3746(8) 7084(8) 4161(5) 326(12) 4761(11) 4263(6) 520(10) 1032(9) 799(6)
36(1) 35(1) 41(1) 46(1) 43(1) 39(1) 45(1) 37(3) 36(2) 41(3) 41(3) 38(3) 49(3) 68(3) 54(3) 83(5) 51(4) 86(3) 53(3) 81(5) 42(1) 38(3) 33(2) 40(2) 37(3) 46(3) 56(3) 75(5) 65(4) 103(4) 69(3) 109(6) 54(4) 76(3) 58(4) 48(3)
Pt(1) Pd(2) P(1) P(2) P(3) P(4) N(3) C(2) N(1) C(6) C(5) C(4) N(7) C(8) N(9) C(3) O(2) C(1) O(6) S(8) N(13) C(12) N(11) C(16) C(15) C(14) N(17) C(18) N(19) C(13) O(12) C(11) O(16) S(18) C(012) C(034)
[(dppm)Pt(µ-TT)2Pd(dppm)]‚7H2O 6788(1) -1202(1) 2928(1) 8484(1) -2854(1) 2655(1) 6953(2) -215(2) 3535(1) 5974(2) -1467(2) 3636(1) 8367(2) -4183(2) 2638(1) 9207(2) -3300(2) 3354(1) 7853(7) -2015(7) 556(4) 8629(11) -2130(10) 363(6) 9184(7) -2435(7) 726(5) 9060(9) -2618(7) 1276(5) 8248(8) -2471(7) 1443(5) 7690(8) -2210(8) 1096(5) 7872(6) -2569(6) 1952(3) 7108(8) -2326(7) 1869(5) 6948(7) -2105(7) 1341(4) 7238(12) -1684(14) 183(7) 8817(8) -1960(9) -107(4) 10016(9) -2542(10) 507(7) 9608(6) -2854(6) 1568(4) 6396(2) -2282(2) 2394(1) 8249(7) 76(6) 1107(4) 7595(11) 425(9) 880(6) 6886(7) 404(7) 1172(5) 6742(9) -6(8) 1671(5) 7468(7) -350(7) 1873(5) 8181(7) -295(6) 1600(5) 7599(6) -799(5) 2336(4) 8394(7) -977(6) 2310(5) 8776(6) -689(6) 1865(4) 8977(10) 25(10) 782(6) 7623(7) 755(7) 431(4) 6179(11) 822(11) 942(8) 6052(6) -60(6) 1852(4) 8874(2) -1553(2) 2812(1) 6367(8) -698(8) 4082(5) 9157(8) -4334(7) 3159(5)
29(1) 29(1) 39(1) 38(1) 37(1) 37(1) 52(3) 65(4) 51(3) 42(3) 37(3) 41(3) 33(2) 38(3) 47(3) 93(7) 90(4) 68(5) 57(3) 45(1) 45(3) 61(4) 48(3) 50(3) 36(3) 35(3) 34(2) 35(3) 40(3) 65(5) 75(3) 83(6) 64(3) 44(1) 44(3) 42(3)
Table 3. Phosphorus-31 NMR Dataa compound
δA
δX
1
JA
-42.7 [Pt(HTT)2(dppm)] (1) [Pd(HTT)2(dppm)] (2) -32.1 [Pt(µ-TT)(dppm)]2 (3) -53.2 -46.0 2830 [Pd(µ-TT)(dppm)]2 (4) -39.9 -31.5 [(dppm)Pt(µ-TT)2Pd(dppm)] (5) -40.3 -32.0 2839 -53.1 -45.8 [(dppm)Pt(µ-TT)2Pt(bipy)] (6) -52.9 -46.3 2820 [(dppm)Pt(µ-TT)2Pd(bipy)] (7) -53.2 -45.9 2832 a
1
JX
2
J
2683 2430 68 97 2428 68 97 2428 69 2428 69
DMSO-d6 solutions, external reference 85% H3PO4.
found for other M(dppm)(dithiolates) (M ) Pd and Pt).10 In view of all this, the compounds should be formulated as cis[M(dppm)(HTT-S(8))2]. On reacting cis-[M(dppm)Cl2] with Na2TT (prepared in situ from the reaction of H2TT and NaOH) in ethanol and 1:1 molar ratio, the dinuclear complexes 3 and 4, of empirical formula [M(TT)(dppm)], are obtained. The IR spectra show neither N-H nor S-H bands, suggesting the coordination of the anion in bidentate fashion. Clear evidence for this mode of coordination can be derived from the 31P-NMR spectra (Table 3), since they consists of AX doublets with 2JPPcis coupling that is appropriate to Pt(II) and Pd(II) complexes10 (Figure 1). In the case of the platinum complex (3), satellites due to 1JPtP couplings with 195Pt are also apparent (Figure 1b). The two 1J values, which are in the usual range for Pt(II), are quite different, with the larger value being assigned to the phosphorous trans to nitrogen on the basis of the Pt-P bond distances in [Pt(µ-TT)(dppm)]2, the shorter distance being associated with the larger coupling constant. The S,N-coordinated TT2- ligand would act in either chelate or bridging mode to form mononuclear or oligomeric species, respectively. Nevertheless, because of geometric requirements, the latter coordination mode is generally favored over the former.4c The results of the X-ray structure determination for [Pt(µ-TT)(dppm)]2‚2DMSO reveals the coordination mode expected from the spectroscopic data. The structure consists of dinuclear [Pt(µ-TT)(dppm)]2 molecules, having a pseudo-2-fold axis perpendicular to that defined by the platinum atoms (see Figure 2), and two DMSO crystal solvent molecules. The two halves of the dinuclear units are chemically but not crystallographically equivalent. Inside the dinuclear molecule, the two platinum atoms are bibridged by (10) (a) Bates, P. A.; Hursthouse, M. B.; Kelly, P. F.; Woolins, J. D. J. Chem. Soc., Dalton Trans. 1986, 2367. (b) Verkade, J. G.; FazlurRahman, A. K. Inorg. Chem. 1992, 31, 5331.
Pt(II) and/or Pd(II) Complexes of H2TT
Inorganic Chemistry, Vol. 36, No. 8, 1997 1655 Table 4. Selected Bond Lengths (Å) and Angles (deg) for 3 and 5 [(dppm)Pt(µ-TT)2Pt(dppm)]‚2DMSO [(dppm)Pt(µ-TT)2Pd(dppm)]‚7H2O Pt(1)-N(17) Pt(1)-P(2) Pt(1)-P(1) Pt(1)-S(8) Pt(2)-N(7) Pt(2)-P(4) Pt(2)-P(3) Pt(2)-S(18) C(8)-N(7) C(8)-N(9) S(8)-C(8) S(18)-C(18) C(18)-N(19) C(18)-N(17)
2.057(9) 2.235(3) 2.270(3) 2.356(3) 2.075(9) 2.236(3) 2.262(3) 2.349(3) 1.344(14) 1.366(14) 1.760(12) 1.741(12) 1.355(14) 1.370(14)
Pt(1)-N(17)a Pt(1)-P(2) Pt(1)-P(1) Pt(1)-S(8) Pd(2)-N(7)a Pd(2)-P(4) Pd(2)-P(3) Pd(2)-S(18) C(8)-N(7) C(8)-N(9) C(8)-S(8) C(18)-S(18) C(18)-N(19) C(18)-N(17)
2.090(10) 2.238(3) 2.259(3) 2.349(3) 2.052(9) 2.221(3) 2.277(3) 2.343(3) 1.35(2) 1.37(2) 1.742(13) 1.761(12) 1.35(2) 1.35(2)
N(17)-Pt(1)-P(2) N(17)-Pt(1)-P(1) P(2)-Pt(1)-P(1) N(17)-Pt(1)-S(8) P(2)-Pt(1)-S(8) P(1)-Pt(1)-S(8) N(7)-Pt(2)-P(4) N(7)-Pt(2)-P(3) P(4)-Pt(2)-P(3) N(7)-Pt(2)-S(18) P(4)-Pt(2)-S(18) P(3)-Pt(2)-S(18) N(7)-C(8)-S(8) N(17)-C(18)-S(18) P(1)-C(012)-P(2) P(4)-C(034)-P(3)
171.8(3) 99.2(3) 73.35(12) 90.8(2) 96.37(11) 168.91(11) 172.5(3) 99.6(3) 73.35(12) 90.5(3) 96.28(11) 168.26(11) 123.2(9) 123.7(9) 94.8(6) 93.5(5)
N(17)-Pt(1)-P(2) N(17)-Pt(1)-P(1) P(2)-Pt(1)-P(1) N(17)-Pt(1)-S(8) P(2)-Pt(1)-S(8) P(1)-Pd(1)-S(8) N(7)-Pd(2)-P(4) N(7)-Pd(2)-P(3) P(4)-Pd(2)-P(3) N(7)-Pd(2)-S(18) P(4)-Pd(2)-S(18) P(3)-Pd(2)-S(18) N(7)-C(8)-S(8) N(17)-C(18)-S(18) P(1)-C(012)-P(2) P(4)-C(034)-P(3)
171.1(3) 97.5(3) 73.53(12) 92.9(3) 96.00(12) 169.15(12) 172.3(3) 100.3(3) 73.64(12) 92.8(3) 92.91(12) 165.97(12) 122.6(10) 122.1(9) 94.3(6) 94.4(6)
a Positions of Pt(1) and Pd(2) are both occupied by Pt and Pd ions at ca. 50%.
Figure 1. 31P-NMR spectra: (a) [Pd(µ-TT)(dppm)]2‚3H2O (4), (b) [Pt(µ-TT)(dppm)]2‚2DMSO (3), and (c) [(dppm)Pt(µ-TT)2Pd(dppm)]‚7H2O (5).
Figure 2. View of the dinuclear unit of 3. Hydrogen atoms, solvent molecules, and phenyl rings have been omitted for clarity.
two µ-TT ligands, in a head to tail arrangement, with Pt-N bond distances of 2.057 and 2.075 Å and Pt-S bond lengths of 2.356 and 2.349 Å. It should be noted that cleavage of a PtS(8) bond in the mononuclear precursor [Pt(HTT-S(8))2(dppm)] is needed to give a head to tail arrangement of the purine ligands in the dinuclear complex; however, this process should be very rapid since it has not been detected by NMR spectroscopy. The square-planar coordination of the Pt(II) atom is completed by a chelate dppm ligand, the platinum atoms being deviated from
the mean coordination plane by 0.0807 and 0.0851 Å. The P-Pt bond distances trans to nitrogen (2.235 and 2.236 Å) are shorter than those trans to sulfur (2.262 and 2.270 Å), as expected. Owing to the geometric requirements of the chelate dppm ligand some of the coordination bond angles considerably differ from the ideal value of 90°. The Pt‚‚‚Pt distance (4.212 Å) is much longer than the sum of the van der Waals radii, so that the metal-metal interaction can be discarded. As the N‚‚‚S bite distance in the TT2- ligand is not much different from those observed for other S,N-bridging ligands in dinuclear platinum(II) complexes with metal-metal interaction,11 the steric repulsions between the bulky dppm ligands must be the main factor precluding metal-metal interaction in this compound. Owing to these interligand steric repulsion within the molecules the coordination planes splay apart by a dihedral angle of 69.2°. Finally, bond distances and angles in the thiotheophyllinato ligand do not significantly differ from those observed for other complexes also containing this S,N-bridging ligand.4 The nine atoms of the purine system are almost coplanar as expected. It should be noted that the reaction of [M(µ-TT)(dppm)]2 with H2TT in ethanol and a 1:1 molar ratio leads to the mononuclear complexes [M(HTT)2(dppm)]. Noteworthy, the dinuclear complexes can be re-formed by reacting the latter with cis[M(dppm)Cl2] and NaOH in 1:1:2 molar ratio (see Scheme 1). This reaction may be monitored by 31P{1H}-NMR spectroscopy in DMSO-d6. In the absence of base, the spectrum of the crude reaction mixture, which does not change with time, indicates an equilibrium between the reagents and the dinuclear compound 3. It is noticeable that no other compounds are present. The equilibrium is pushed to the formation of 3 when NaOH is added to the crude reaction mixture. On the other hand, when NaOH is added to a solution of 1, no reaction was seen, which indicates (11) Umakoshi, K.; Kinoshita, I.; Ichimura, A.; Ooi, S. Inorg. Chem. 1987, 26, 3351.
1656 Inorganic Chemistry, Vol. 36, No. 8, 1997 that, for the formation of 3, both 1 and [M(dppm)Cl2] are needed. This fact prompted us to explore the reactions between the mononuclear complexes and [M(L-L)Cl2] (M ) Pt(II) and Pd(II), and L-L ) dppm and 2,2′-bipyridine) in order to obtain homo- and heterodinuclear complexes. Following this procedure we have succeeded in obtaining the complexes [(dppm)Pt(µ-TT)2M(L-L)] (5-7). The IR spectra of these complexes are very similar to, almost identical with, those of 3 and 4, thus suggesting the same S(8),N(7)-bridging mode in all of them. This is supported by the crystal structure results for 5. The structure of this compound consists of dinuclear [(dppm)Pt(µTT)2Pd(dppm)] units and seven lattice crystal water molecules. The dinuclear entities are almost superimposable to those of 3 (Table 4), by which the structure of the dinuclear unit of 5 can be seen as that of 3 with an isomorphic substitution of one of the Pt(II) ions by a Pd(II) ion, the metal ions being disordered in both positions by ca. 50%. Nevertheless, some minor differences are found for the relative positions of the purine ligands which are attributed to the existence on an extended hydrogen bond network involving the seven water molecules and the heteroatoms of the purines. In this complex the Pt‚‚‚Pd distance of 4.034 Å is shorter by ca. 0.2 Å than that of 3 as
Colacio et al. a consequence of a decrease in the dihedral angle between the coordination planes (65.9°). Remaining bond distances and angles fall well within their usual range and do not deserve further comments. In good accord with the structure the 31PNMR spectrum of 5 exhibits two groups of AX doublets (Figure 1c), arising from the Pd(II) and the Pt(II) fragments of the dinuclear molecule, respectively. The spectra of 6 and 7 are very similar to that of 3, as expected. In view of the ability of the H2TT ligand to form homo- and heterodinuclear complexes, we have decided to extend our work by using other M(II) pairs and/or less sterically hindered ligands which might allow the metal-metal interaction. Work along this line is in progress. Acknowledgment. The authors gratefully acknowledge financial aid from Junta de Andalucı´a. Supporting Information Available: Full listings of crystal data and structure refinement, fractional atomic coordinates, thermal parameters, and bond lengths and angles (23 pages). Ordering information is given on any current masthead page. IC961288P
